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2012 , Vol. 32 >Issue 11: 2122 - 2128

DOI: https://doi.org/10.6023/cjoc201205034

研究论文

2-酯基-1,5-苯并氧氮杂(艹卓)的合成及反应副产物的研究

  • 刘倩 ,
  • 赵利飞 ,
  • 李文红 ,
  • 李媛
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  • a 河北师范大学化学与材料科学学院 石家庄 050024;
    b 河北工业职业技术学院环境与化学工程系 石家庄 050091

收稿日期: 2012-05-29

  修回日期: 2012-07-11

  网络出版日期: 2012-07-17

基金资助

国家自然科学基金(No. 20972040)资助项目.

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Synthesis of 2-Ester-substituted-1,5-benzoxazepines and Studies on the By-product in the Reaction

  • Liu Qian ,
  • Zhao Lifei ,
  • Li Wenhong ,
  • Li Yuan
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  • a College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024;
    b Environment and Chemical Engineering, Hebei College of Industry and Technology, Shijiazhuang 050091

Received date: 2012-05-29

  Revised date: 2012-07-11

  Online published: 2012-07-17

Supported by

Project supported by the National Natural Science Foundation of China (No. 20972040).

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摘要

以取代苯、丁烯二酸酐、邻氨基(对氯邻氨基)苯酚为原料, 合成了一系列2-酯基-1,5-苯并氧氮杂(艹卓)衍生物, 其结构通过IR, 1H NMR, MS (HRMS)及元素分析进行表征. 同时, 确定了一个主要副产物2-苯甲酰甲基-2H-1,4-苯并噁嗪- 3(4H)-酮(6h')的结构, 提出了其可能的生成机理. 研究还表明, 中间体4-芳基-4-氧代-2-丁烯酸酯(4)在对甲基苯磺酸为催化剂、DMF作溶剂、回流温度下反应时主要生成目标产物2-酯基-1,5-苯并氧氮杂(艹卓)6, 而在冰醋酸为催化剂、甲醇作溶剂、回流温度下反应时则主要生成副产物6h'.

关键词： 迈克尔加成; 1,5-苯并氧氮杂(艹卓); 2-氨基苯酚; 4-氯-2-氨基苯酚; 反应机理

本文引用格式

刘倩 , 赵利飞 , 李文红 , 李媛 . 2-酯基-1,5-苯并氧氮杂(艹卓)的合成及反应副产物的研究[J]. 有机化学, 2012 , 32(11) : 2122 -2128 . DOI: 10.6023/cjoc201205034

Abstract

A series of new 1,5-benzoxazepines have been synthesized from substituted benzene, maleic anhydride and 2-aminophenol (4-chloro-2-aminophenol) and identified by IR, 1H NMR, MS (HRMS) techniques and elemental analysis. Meanwhile, the structure of one main by-product 2-benzoylmethyl-2H-1,4-benzoxazin-3(4H)-one (6h') was identified, and the possible mechanism of producing the by-product was proposed. The optimization of reaction conditions showed that the reactions were performed in DMF solvent, at refluxed temperature and catalyzed by p-toluenesulfonic acid, and 2-ester-sub-stituted-1,5-benzoxazepines 6 were the main products. While, the reactions were performed in methyl alcohol, at refluxed temperature and catalyzed by acetic acid, and the by-product 6h' was formed in good yield.

Key words： Michael addition; 1,5-benzoxazepine; 2-aminophenol; 4-chloro-2-aminophenol; reaction mechanism

参考文献


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